EP0826628B1 - Gels de SiCN comme précurseurs de céramiques au silicium non oxydées - Google Patents

Gels de SiCN comme précurseurs de céramiques au silicium non oxydées Download PDF

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Publication number
EP0826628B1
EP0826628B1 EP97114240A EP97114240A EP0826628B1 EP 0826628 B1 EP0826628 B1 EP 0826628B1 EP 97114240 A EP97114240 A EP 97114240A EP 97114240 A EP97114240 A EP 97114240A EP 0826628 B1 EP0826628 B1 EP 0826628B1
Authority
EP
European Patent Office
Prior art keywords
sicn
gels
precursors
alkyl
oxide silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97114240A
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German (de)
English (en)
Other versions
EP0826628A1 (fr
Inventor
Ralf Prof. Dr. Riedel
Andreas Gabriel
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Bayer AG
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Bayer AG
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Publication of EP0826628B1 publication Critical patent/EP0826628B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/0213—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/455—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used

Definitions

  • the invention furthermore relates to the use of the SiCN gels according to the invention for the production of ceramic powders, coatings, moldings, fibers and membranes and for the infiltration of porous substrates.
  • SiCN gels according to the invention are silyl carbodiimides of the type R 3 Si-NCN-SiR 3 , where R symbolizes an alkyl or aryl group, in particular a methyl, ethyl or phenyl group, and (alkyl) trihalosilanes of the type RSiX 3 , where R can be a hydrogen atom or an alkyl or aryl group, in particular a methyl, ethyl, propyl, isopropyl or phenyl group, and X represents fluorine, chlorine, bromine or iodine.
  • the formation of the SiCN gels according to the invention is catalyzed by the addition of a base. Pyridine is added as a catalyst in amounts of 0.01 to 1.5 equivalents, based on the molar amount of (alkyl) trihalosilane.
  • the SiCN gels according to the invention are formed after the following gross reaction: n RSiX 3 + 1.5n R ' 3 Si-NCN-SiR' 3 ⁇ [RSi (NCN) 1.5 ] n + 3n R ' 3 SiX
  • the invention SiCN gels produced by mixing starting components and catalyst and the mixture is stirred until the gel point is reached.
  • the reaction time depends on the amount of base added, the reaction temperature and the stirring speed. As a rule, it is between 10 minutes and 15 hours. Expediently the temperature for the reaction to a value between room temperature and about 80 ° C to adjust.
  • reaction is carried out at room temperature without stirring carried out.
  • the required reaction time is naturally longer and longer can be up to several weeks.
  • SiCN gels according to the invention can also be used in inert solvents such as THF, diethyl ether or toluene can be carried out.
  • the SiCN gels according to the invention can be subjected to a drying step in which volatile reaction products, catalyst and, if appropriate, solvent are removed. This is preferably done under reduced pressure, at room temperature or at elevated temperature.
  • a xerogel is obtained which, depending on the drying conditions, is obtained in compact or powder form.
  • a special feature of this xerogel is its low porosity; the accessible surface is less than 1, preferably even less than 0.1 m 2 / g (determined by BET measurements).
  • the SiCN gels according to the invention are left aging at temperatures up to 54 ° C before the drying step, whereby a three-dimensional shrinking process takes place. This is with gel layers completed after several minutes to a few hours while at Shaped bodies lasts about 5 days to 8 weeks. After drying can be so Obtained transparent, crack-free molded body made from Xerogel.
  • the SiCN gels according to the invention can be used prior to aging / drying various molding processes such as casting, extrusion, fiber drawing etc. be subjected. In this way, after subsequent pyrolysis ceramic coatings, monolithic moldings and composites, fibers or obtained membranes.
  • the SiCN gels according to the invention are also suitable for the infiltration of porous substrates, which can consist of ceramics or carbon, for example.
  • the SiCN gels according to the invention then form in situ and fill the pores of the substrate.
  • the conversion of the SiCN gels according to the invention to non-oxide silicon ceramics takes place by pyrolysis in an inert atmosphere, e.g. Argon, helium, nitrogen or in a reactive atmosphere, e.g. Ammonia.
  • an inert atmosphere e.g. Argon, helium, nitrogen or in a reactive atmosphere, e.g. Ammonia.
  • the pyrolysis temperature can be up to 1400 ° C if an amorphous ceramic is to be produced. From about The product crystallizes out at 1450 ° C.
  • the thermally induced ceramization of the xerogel was performed using simultaneous Thermal analysis (STA) in the temperature range between room temperature and 1500 ° C in He examined. As a result, the ceramic yield was 60%. in the Temperature range of 560 - 590 ° C, a mass loss of 20% was accompanied from an exothermic reaction.
  • Toluene as the solvent is placed in a quartz vessel. In this one porous substrate immersed, or it becomes a ceramic powder to be coated suspended in it. Subsequently, starting components in stoichiometric Ratio and catalyst added and it is heated to boiling. After the reaction, the liquid components are reduced Distilled off pressure, and the polymer-coated substrate is pyrolyzed at 1000 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)
  • Catalysts (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Colloid Chemistry (AREA)

Claims (2)

  1. Gel de SiCN qui peut être obtenu par réaction de silylcarbodiimides R3Si-N=C=N-SiR3 (R = alkyle, aryle) avec des silanes RSiX3 (R = H, alkyle, aryle ; X = F, Cl, Br, I) avec addition de bases.
  2. Utilisation des gels de SiCN selon la revendication 1 pour la production de poudres céramiques, de revêtements, de pièces mises en forme, de fibres et de membranes ainsi que pour l'infiltration de substrats poreux.
EP97114240A 1996-08-29 1997-08-18 Gels de SiCN comme précurseurs de céramiques au silicium non oxydées Expired - Lifetime EP0826628B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19634799A DE19634799A1 (de) 1996-08-29 1996-08-29 SiCN-Gele als Vorstufen zu nichtoxidischen Silicium-Keramiken
DE19634799 1996-08-29

Publications (2)

Publication Number Publication Date
EP0826628A1 EP0826628A1 (fr) 1998-03-04
EP0826628B1 true EP0826628B1 (fr) 2000-01-26

Family

ID=7803944

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97114240A Expired - Lifetime EP0826628B1 (fr) 1996-08-29 1997-08-18 Gels de SiCN comme précurseurs de céramiques au silicium non oxydées

Country Status (4)

Country Link
US (1) US5863462A (fr)
EP (1) EP0826628B1 (fr)
JP (1) JPH10114574A (fr)
DE (2) DE19634799A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19706028C1 (de) * 1997-02-17 1998-07-02 Bayer Ag Neue Carbodiimid-Polymere als Vorstufen für C/N- und B/C/N-Werkstoffe
JP2005500969A (ja) 2001-08-28 2005-01-13 ツェアー、アンドレアス スピネル構造を有するシリコンカルボニトリド
US6774432B1 (en) * 2003-02-05 2004-08-10 Advanced Micro Devices, Inc. UV-blocking layer for reducing UV-induced charging of SONOS dual-bit flash memory devices in BEOL
US7118967B1 (en) 2003-02-19 2006-10-10 Spansion, Llc Protection of charge trapping dielectric flash memory devices from UV-induced charging in BEOL processing
US6989563B1 (en) 2004-02-02 2006-01-24 Advanced Micro Devices, Inc. Flash memory cell with UV protective layer
US7091088B1 (en) 2004-06-03 2006-08-15 Spansion Llc UV-blocking etch stop layer for reducing UV-induced charging of charge storage layer in memory devices in BEOL processing
US20060084566A1 (en) * 2004-10-19 2006-04-20 General Electric Company Multiphase ceramic nanocomposites and method of making them
DE502008002416D1 (de) * 2008-10-16 2011-03-03 Looser Holding Ag Antihaft-Beschichtungen
JP2010174133A (ja) * 2009-01-29 2010-08-12 Teijin Ltd ポリシリルカルボジイミド化合物およびその製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4594330A (en) * 1984-03-22 1986-06-10 Mitsubishi Gas Chemical Company, Inc. Fine amorphous powder and process for preparing fine powdery mixture of silicon nitride and silicon carbide
US4704299A (en) * 1985-11-06 1987-11-03 Battelle Memorial Institute Process for low temperature curing of sol-gel thin films
FR2640952B1 (fr) * 1988-11-25 1991-03-01 Rhone Poulenc Chimie
US5306555A (en) * 1991-09-18 1994-04-26 Battelle Memorial Institute Aerogel matrix composites
CA2138489A1 (fr) * 1993-12-17 1995-06-18 Masanori Okabe Poudre de composite a base d'yttrium, corps fritte composite, et methode pour l'obtenir.
JP2793773B2 (ja) * 1994-05-13 1998-09-03 神鋼コベルコツール株式会社 耐摩耗性に優れた硬質皮膜、硬質皮膜被覆工具及び硬質皮膜被覆部材
DE4430817C2 (de) * 1994-08-30 1997-02-13 Max Planck Gesellschaft Herstellung keramischer Materialien durch Pyrolyse von hochvernetzten polymeren Carbodiimiden als Keramikvorstufe sowie Keramikvorstufe
DE19502095A1 (de) * 1995-01-24 1996-07-25 Max Planck Gesellschaft Herstellung keramischer Überzüge durch reaktive Abscheidung von polymeren Keramikvorstufen

Also Published As

Publication number Publication date
DE59701060D1 (de) 2000-03-02
US5863462A (en) 1999-01-26
JPH10114574A (ja) 1998-05-06
DE19634799A1 (de) 1998-03-05
EP0826628A1 (fr) 1998-03-04

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